Diethers and copolymerizates therefrom



United States Patent 3,327,019 DIETHERS AND COPOLYMERIZATES THEREFROM Helmut Mylenbusch and Heinrich Krimm, Krefeld- Bockum, and Herman Schnell, Krefeld-Urdingen, Germany, assignors to Farhenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany. No Drawing. Filed Feb. 1, 1966, Ser. No. 523,956 Claims priority, application Germany, Nov. 24, 1960, F 32,612; Apr. 19, 1961, F 33,705; Dec. 16, 1961, F 35,574; Feb. 6, 1962, F 35,943

9 Claims. (Cl. 260-861) This application is a continuation-in-part of applications Ser. No. 154,021 filed Nov. 21, 1961, Ser. No. 243,- 666 filed Dec. 10, 1962 and Ser. No. 255,108 filed Ian. 30, 1963, each of the aforesaid applications being now abandoned.

The present invention is concerned with new diethers and copolymerizates therefrom. The reaction scheme utilized to produce these novel diethers and copolymerizates can be illustrated as follows:

production of novel diether III.

I copolymerizable RO-CHzCH-CH2OR compound production of novel copolymerizate The definitions of R and R above are explained in detail below.

The new diethers of the present invention are represented by the general formula:

wherein R R and R are the same or different and signify hydrogen or alkyl having up to 4 carbon atoms, cycloalkyl or phenyl, R and R which may also be the same or different, signify hydrogen atoms or methyl, R signifies a radical with n substitutable positions on aromatic nuclei, and n is a whole number greater than zero. The novel diethers according to the present invention are identified as Z-hydroxy-l-(p-vinylphenyl)-3-arylpropylene diethers. The new diethers may be obtained by reacting at least n mols of a p-vinylphenylglycidyl either of the general formula:

copolyrnerizate wherein R R R R and R have the same meanings as above, with one mol of an appropriate n-basic aromatic hydroxyl compound, optionally in the presence of inert organic solvents and catalysts.

Surprisingly, the vinyl group of the p-vinylphenylglycidyl ether is not thereby affected, although it is known that phenols, namely in the presence of acidic or basic catalysts, readily react with aliphatic double bonds, for example, with the formation of alkylated phenols or of phenol ethers.

Patented June 20, 1967 As examples of p-vinylphenyl-glycidyl ethers which may be used to produce the novel diethers of the present invention, there may be mentioned the ethers of vp- Z-methyll-ethyl-vinyl) -phenol,

p-(2-ethyl-1-ethyl-vinyl) -phenol, p-(2-propyl-1-ethyl-vinyl) -phenol, p-(2-isopropyl-l-ethyl-vinyl)-phenol, p-( l-propyl-vinyl) -phenol,

p- (Z-methyll-propyl-vinyl -phenol, p- (2-ethyl-l-propyl-vinyl -phenol, p-( l-isopropyl-vinyl) -phenol,

p-( l-butyl-vinyl) phenol,

p( l,Z-tetramethylene-vinyl) -phenol, p-( l-cyclohexyl-vinyl) -phenol,

p-( l-phenyl vinyl -phenol,

p-( l-methyl-vinyl) -o-cresol, and so on.

In order to produce the glycidyl ethers useful as starting materials one may use the known reaction of phenols with epihalohydrins in the presence of tertiary amines to give the corresponding halohydrin-phenyl ethers and the splitting of hydrogen halide therefrom with alkali to form phenyl glycidyl ethers. Alternatively one may use the reaction of phenols with epihalohydrins or dihalohydrins in the presence of alkalis to give directly the corresponding phenylglycidyl ethers. Any one of the following equations:

may be used wherein ROH stands for a p-vinylphenol of the general formula:

wherein R R R R and R are as defined above. By the use of these reactions therefore the p-vinylphenylglycidyl ethers used as starting materials for the diethers of the present invention can be obtained.

As is known from the reaction of vinyl group-free phenols with epihalohydrins or dihalohydrins, the p-vinylphenols can, according to the invention, also be reacted to produce the p-vinylphenyl glycidyl ether in different ways.

Thus, for example, a catalytic amount of a tertiary amine can be added to a solution of a p-vinylphenol in excess epihalohydrin, the solution, starting at room temperature, slowly heated and then the equivalent amount of aqueous alkali added at temperatures between about 20 and 100 C.

Another form of the process consists in adding dropwise, at temperatures between about 20 and about 40 0., excess epihalohydrin or di halohydrin to the solution of the p-vinylphenol in aqueous alkali. Furthermore, a cold solution of a p-vinylphenol in epihalohydrin or dihalohydrin can be added to an aqueous alkali solution at about 70 100 C. or, on the one hand, such a solution and, on the other hand, an aqueous alkali solution can be introduced gradually and simultaneously into a reaction vessel heated to about 70100 C.

If desired, it is also possible to deviate from the abovementioned temperatures. In general, however, suitable reaction temperatures lie in the region between about 0 and about 100 C., and particularly between 20 and 80 C.

As vinylp henols used to produce the p-vinylphenylglycidyl ethers, the following vinylphenols may, for example, be mentioned:

p-vinylphenol,

p- (Z-methyl-vinyl) -phenol,

p- (2-ethyl-vinyl) phenol,

p-( 2,2-dimethyl-vinyl) -phenol,

p- 2-propyl-vinyl) -phenol,

p- 2-isopropyl-vinyl) -phenol,

p- Z-butyl-vinyl -phenol,

p- (2-methyl-2-propyl-vinyl -phenol,

p- (2-methyl-2-isopropyl-vinyl) -pheno1,

p- 2,2-diethyl-vinyl -phenol,

p- 2-eflhy1-2-isopropyl-vinyl) -phenol,

p-( l-methyl-vinyl) -phenol (p-isopropenyl-phenol p- Z-met-hyll-methyl-vinyl) phenol (p-isobutenylphenol) p- Z-ethyl- 1 -methyl-vinyl) -phenol,

p- 2,2-dimethyl- 1 -methyl-vinyl -phenol,

p- 2-propyll-methyl-vinyl -phenol,

p-(2-isopropyl-1-methyl-vinyl) -phenol,

p-( 1-ethyl-vinyl) -phenol,

p- Z-methyl- 1 -ethyl-vinyl) -phenol,

p-(2-et'hyl-1-ethy1-vinyl)phenol,

p- 2-propyll-ethyl-vinyl -phen 01,

p-( 2-isopropyll-ethyl-vinyl) -phenol,

p-(1-propyl-vinyl)-phenol,

p- (Z-methyll-propyl-vinyl) -phenol,

p-(2-ethyl-1-propyl-vinyl) phenol,

p-( l-isopropyl-vinyl -phenol,

p-( 1,Z-tetramethylene-vinyl) phenol,

p-( 1-phenyl-vinyl)-phenol and p-( l-methyl-vinyl) -o-cresol etc. 7

The p-vinylphenols, especially the particularly valuable p-isopropenyl phenol, are obtainable, for example, by catalytic fission of the corresponding dihydroxy-diaryl alkanes, particularly with the use of alkaline materials 4 as fission catalysts according to the process of the U.S. specification Ser. No. 44,848.

As epihalohydrins or dihalohydrins, the chlorine and bromine products can be used with advantage. As tertiary amines which can, if desired, be used for the process, there may be mentioned by way of example, triethylamine, dimethyland diethylaniline, dimethyland diethylcyclohexylamine, triphenylamine and pyridine.

Aromatic monoand polyhydroxyl compounds which can be reacted with the p-vinylphenyl-glycidyl ethers according to the invention are, for example, phenol, alkylphenols, such as the cresols, the xylenols, monoand polyethylphenols, monoand polypropylphenols and so on, cycloalkylphenols, such as cyclohexylphenols, halophenols, such as monoand p-olychloro, bromo and idophenols, nitrophenols, dihydroxybenzenes, such as hydroquinone and resorcinol, dihydroxydiphenyl, dihydroxydiphenyl-alkanes, -cycloalkanes, ethers, sulphides, sulphoxides and sulphones of the bis-(4-hydroxyphenyl) methane type or of the 2,2-bis(4-hydroxyphenyl) propane type, as well as a,a'-di-(4-hydroxyphenyl)-u,a,a,a'- tetramethyl-p-xylene, the triphenol of the formula:

which is obtainable by the treatment of p-isopropenylphenol with acidic catalysts, 1-p-hydroxyphenyl-3,3-di-phydroxyphenyl propane and 1,l,2,2-tetra-(p-hydroxyphenol)-ethane.

R can represent the residue of an aromatic hydroxy compound which is a mixed .polymerizate of p-isopropenyl phenol with other polymerizable vinyl compounds, such as are obtainable by the reaction of p-vinylphenols with vinyl monomers, such as styrene, in the presence of Lewis acids. Also condensation products from phenols and aldehydes of the novolak type or resols can be used. In such cases the number of hydroxy groups will depend on the number of repeating polymer units.

The addition of the aromatic monoand polyhydroxy compounds to the p-vinylphenyl-glycidyl ethers can according to the invention take place not only in the melt of the reaction components but also in an inert solvent, such as chlorobenzene, toluene, xylene, ethyl-benzene, decahydronaphthalene, anisol, diethyl carbonate or pyridine, at temperatures between about 50 and about 250 C.

For the acceleration of the reaction, there can be added, if desired, catalysts, such as alkali metal hydroxides, alkali metal acetates, alkali metal stearates, alkali metal oleates and alkali metal phenolates, as well as tertiary amines, such as pyridine,triethyl amine,dimethylcyclohexylamine and dimethylaniline, and also triphenyl phosphine, preferably in amounts of about 0.001 to about 10%.

In order to obtain the products in as colorless a form as possible, it is advisable to work in inert atmospheres, such as atmospheres of nitrogen, hydrogen or carbon dioxide.

For the quantitative etherification of the phenolic hydroxyl groups, it is expedient to add an excess of the glycidyl ether which, if desired, can again be removed from the reaction product by distillation.

Instead of using an excess of glycidyl ether, it is, however, also possible, if desired, to etherify free phenolic hydroxyl groups still present in the end product by the addition of simple epoxides, such as ethylene oxide, propylene oxide and styrene oxide. The content of free phenolic hydroxyl groups in the addition products can be determined chromatographically or by color reactions.

On the basis of the reactive aliphatic hydroxyl groups which may be present several times in the new ethers, as well as on the double bonds, these products are intermediates of wide applicability, for example, for the production of plasticizers and of polymerizable esters and polyesters by methods known in the art per se.

The new copolymerizates of the present invention may be obtained by copolymerizing the 2-hydroxy-l-(p-vinylphenyl)-3-arylpropylene diethers with polymerizable compounds.

Examples of polymerizable compounds for copolymerization with the 2-hydroxy-1-(p-vinylphenyl)-3-arylpropylene diethers include vinyl compounds, such as styrene, a-methyl-styrene, chloro-styrenes, acrylic and methacrylic acid nitrile, acrylic and methacrylic acid esters, acrylic and methacrylic acid amide, methyl vinyl ketone, methyl vinyl ether, vinyl acetate, maleic acid and fumaric acid derivatives, such as maleic anhydride or esters of maleic or fumaric acid, as well as unsaturated polyesters which contain, as main components, maleic acid or fumaric acid esters. Mixtures of several such polymerizable compounds may also be used as multiple component systems for copolymerization with the 2-hydroxy-l-(p-vinylphenyl)-3-aryl-propylene diethers.

propylene diethers which leads to cross linkage products.

Even additions of 5 to of a Z-hydroxy-l-(p-vinylphenyl)-3-aryl-propylene diether to a vinyl monomer, such as styrene, leads to the hardening of insoluble and non-meltable formed bodies which possess outstanding mechanical and electrical properties, as well as high heat stability and which are completely insensitive to heat, water, acids or alkalis, even upon storage for several weeks at high temperatures.

The polymerization can be initiated by heat, irradiation or radical-forming polymerization catalysts.

Radical-forming polymerization catalysts are, for example, diacetyl peroxide, dibenzoyl peroxide, lauroyl peroxide, tertiary-butyl peroxide, methyl ethyl ketone hydroperoxide, cyclohexanone hydroperoxide, tertiary butyl hydroperoxide, tertiary butyl peracetate, tertiary-butyl perbenzoate, ditertiary-butyl diperphthalate, peracetic acid, hydrogen peroxide, potassium and ammonium sulfate and azo diiso-butyronitrile.

Cold hardening catalyst systems, such as cobalt II salts/ hydroperoxides and tertiary amines/diacyl peroxides, are also useful catalysts. Furthermore, heat, light and energyrich rays are effective polymerization initiators. Finally, the polymerization can also be carried out according to the anionic or cationic mechanism with corresponding catalysts, in known manner.

The polymerization technique to be chosen in any particular case depends, in the first place, on the nature of the copolymerizates to be produced and on the properties of the reaction components. If the starting materials and the end products are soluble, as is the case with simple unsaturated 2 hydroxy-l-(p-vinylphenyl)-3-aryl-propylene diethers, there can be used, apart from mass polymerization, also solution, dispersion or emulsion polymerization. If the copolymerizates are insoluble and non-meltable, as is the case with multiple unsaturated Z-hydroxyl-(p-vinylphenyl)-3-aryl-propylene diethers, it is advantageous to use mass polymerization.

The properties of the new copolymerizates depend, of course, to a large extent upon the nature and composition of the components. Since these can be varied within the wide limits there is available by the present invention, a considerable breadth of variation of interesting synthetic resins. The new copolymerizates are synthetic resins or, in so far as they are soluble, also intermediate products for the production and modification of synthetic resins, and lacquer raw materials.

If desired, strengthening and filling agents, such as quartz powder, glass fibres, glass woven fabrics, wool and mats, asbestos and metal powder, as well as textiles can be worked in, as well as pigments, dyestuifs and plasticizers.

The exceptional adherence of the hardened resins to glass, metals, wood and other materials is particularly noteworthy. This property proves to be particularly valuable in the case of the incorporation of fillers and strengthening materials. 7

The following examples are given for the purpose of illustration only and are not to be construed as express or implied limitations.

PRODUCTION OF GLYCIDYL ETHER Example 1 A solution of 134 grams (1 mol) p-isopropenylphenol in 277 grams (3 mol) epichlorohydrin, to which 10 grams (0.1 mol) triethylamine are added, is slowly heated to C. with stirring and maintained for A hour at this temperature. 200 millilitres (1 'mol) S'N sodium hy- Example 2 A solution of 134 grams (1 mol) p-isopropenyl phenol in grams (2 mol) epichlorohydrin to which 10 grams (0.1 mol) triethylamine are added, is slowly heated to 90 C. and maintained at this temperature for 1 hour. The reaction mixture is then cooled to 40 C. At this temperature, 210 millitres (1.05 mol) 5 N sodium hydroxide solution are slowly added dropwise, with stirring. The mixture is further stirred for 2 hours at 40 C. The working up takes place as described in Example 1. Yield:

7 167 grams (88 percent of the theory).

Example 3 A solution of 134 grams (1 mol) p-isopropenyl phenol in 200 millilitres (1 mol) 5 N sodium hydroxide solution is added dropwise, with stirring, at room temperature during the course of 1 hour to 450 grams (5 mol) epichlorohydrin. The mixture is further stirred for 10 hours at room temperature. Working up takes place as described in Example l. Yield: 158 grams (78 percent of the theory).

Example 4 -A solution of 134 grams (1 mol) p-isopropenyl phenol in 200 millilitres (1 mol) 5 N sodium hydroxide solution is added dropwise, with stirring, to 277 grams (3 mol) epichlorohydrin previously heated to 90 C. Stirring is carried out for a further two hours at 90 C. Working up takes place as described in Example 1. Yield: 139 grams (73 percent of the theory).

Example 5 A solution of 67 grams (0.5 mol) p-isopropenyl phenol in 200 millilitres (1 mol) 5 N sodium hydroxide solution is added dropwise, with stirring, at 70 C. to a solution 7 8 of 67 grams (0.5 mol) p-isopropenyl phenol in 277 grams PRODUCTION OF NOVEL DIETHER (3 mol) epichlorohydrin. The mixture is further stirred Example 1 for two hours at 90 C. Working up takes place as described in Example 1. Yield: 144 grams (76 percent of the 1 l of 2. -l y r yph nyl)pr p ne 1 6 theory), 5 in a 1 liter flask, provided with a stirrer and an internal Example 6 thermometer, with 2 mols of p-(l-methyl-vmyD-phenyl glycidyl ether (p-isopropenylphenyl glycidyl ether) with 220 inim- (1,1 l 5 N Sodium h id 1 the addition of 0.1% of lithium bisphenolate in an atmostion is added dropwise, with stirring, at 40 C. to a solu- Phere of nltfogen and l y H f Stlfrlng t0 ti f 148 grams (1 l -i b 1 h i 277 130-140" C. An exothermic addit on reaction commences grams (3 mol) epichlorohydrin. The mixture is further in thls f p Iange- Y Suitable Coohng; the stirred for 2 hours at 40 C. Working up takes place as Peratllre 1S alnt lncdbetween 150 and 160 C. rafter d ib d i E l 1, Yi ld of .i b l h l subsidence of the reaction, the m1xtur e is further stirred glycidyl ether: 178 grams (87 percent of the theory). B.P. for 1 110111" at 155 There IS t ln a P Y P 122 125 C /(),2 H 15 colored resin WhlCll 1s hard at room temperature, which softens at 100-110 C. and is readily soluble in most Example 7 organic solvents.

. Molecular weight determination: 590-600 (theoreti- 174 grams (1 mol) p-cyclohexenyl phenol in 460 grams cally 608). The product corresponds to the following (5 mol) epichlorohydrin with the addition of 1 gram tri- 2O formula:

phenyl phosphine are slowly heated to 80 C., with stir- Example 2 ring, and maintained at this temperature for 1 hour, 1.1 mol of a percent sodium hydroxide solution are added dropwise at -60 C. during the course of /2 hour. The reaction mixture is stirred for a further /2 hour at this temperature. The layers are subsequently separated, the organic phase washed once with water and excess epichloat percent of the theory of p cyclohexenyl pheny1 g1ycidy1 ishread ily soluble in most organic solvents. Content of ethfir BIP. 163465, CJO-Z mm Hg. p enohc hydroxyl groups. 0.02%. The product corresponds to the following formula:

1 mol of 1,1-di-(4-hydroxyphenyl)-cyclohexane is heated, with stirring, to a temperature of -130 C., in an atmosphere of hydrogen, with 2.05 mols of p-(l-ethylvinyl)-phenyl glycidyl ether with the addition of 0.1% 39 dimethylcyclohexylamine. The mixture is maintained for 1 hour at 150 C. and then cooled. There is obtained Example 8 A solution of 196 grams (1 mol) p-(a-phenylvinyD- Example 3 phenol in 1.1 mol 15 percent sodium hydroxide solution is added dropwise in the course of 1 hour at 3035 C. to 55 1 mol of 2,6,2,6'-tetrachloro-2,2-di-(4-hydroXy-phen- 460 grams (5 mol) epichlorohydrin to which 1 gram triyl)-propane is dissolved in 1 liter xylene with 2.1 mols of ethylarnine has been added. The reaction mixture is subp-(1-phenylvinyl)-phenyl glycidyl ether, with the addition sequently heated for /2 hour at 70 C. The layers are sepof 0.05% sodium hydroxide, and heated to boiling under arated. The organic phase is washed once with Water and reflux for 3 hours. There is obtained the yellow-colored excess epichlorohydrin distilled off under water pump 60 solution of the addition product which is freed from solvacuum. The residue is fractionated at oil pump vacuum. vent at water pump vacuum. There remains behind a hard Yield: 87 percent of theory of p-(ot-phenylvinyl)-phenylbrittle resin which is reasonably soluble in high boiling glycidyl ether; B.P. -162 C./ 0.05 mm. Hg. organic solvents. It corresponds to the formula:

CH2 C1 3,327,019 9 10 Example 4 um acetate. An exothermic reaction hereby takes place. The mixture is further stirred for 1 hour at 140-150 C. and then cooled. There is obtained a crystalline, greywhite product melts at 140-150 C. and is reasonably soluble in high boiling organic solvents. It corresponds to the following formula:

1 mol of a,a'-di(4-hydroxyphenyl)-a,a,a',a'-tetramethyl-p-xylene is heated in a nitrogen atmosphere, with stirring, to 130-170" C. with 3 mol p-isopropenyl phenylglycidyl ether and with the addition of 0.5% triphenylphosphine. An exothermic addition reaction hereby takes place. The mixture is subsequently stirred for 1 hour at 140 C., then the excess of p-isopropenylphenyl glycidyl H 0 011 ether is distilled off at oil pump vacuum. There remains a behind a yellow, hard resin which softens at 100-110 C. and is readily soluble in most organic solvents. It corre- H3O H Y sponds to the following formula:

I Example5 Example 9 1 mol of 4,4'-dihydroxydiphenyl sulphide is heated in 95 grams of a mixed polymerizate from p-isopropenylan atmosphere of nitrogen, with stirring, at 120-125 C. phenol and styrene (hydroxyl number 112-116) are with 2 mols of p-isopropenyl-phenyl glycidyl ether, with heated f 3 hours at With 38 grams of P- the addition of'0.2% of triphenyl phosphine. An exoisopropenylphenyl glycidyl ether, with the addition of thermic addition reaction hereby takes place. The mix- 0.13'grams of sodium hydroxide. There is obtained a ture is maintained for a further hour at 130-140" C. and Yellow Colored hard resin Which ns at C- and is then cooled. There is obtained an almost colorless crystalreadily soluble in most organic solvents. It corresponds line product which melts at 90-100 C. and is readily to t following formula; soluble in most organic solvents. It corresponds to the- 6 following formula:

Example 6 m 1 mol of 4,4'-dihydroxydiphenyl sulphone is heated m means a whole number greater than 1.

with 2 mols of p-isopropenyl-phenyl glycidyl ether, with E x a m P16 10 the addition of 0.05% potassium hydroxide, in 1 liter.4 toluene for 3 hours under reflux. There is obtained the 180 grams of a novolak Obtained y Polycondfinsation almost colorless solution of the addition product, which of P- and formaldehyde in 3 H101 ratio f 817 in th is freed from solvent at water pump vacuum. There re- Presence of P'toluene rsulphonic acid as catalyst ymains behind a product which crystallizes upon suitable Y equivalent of Said Product is are heated treatment, which melts at 120-130 c. and is reasonably with 290 grams of pp p y p y y y ether soluble in high boiling organic solvents. It corresponds With the addition of gram of Sodium hydrOXide for 3 to the following formula: hours to 160-170 C. under nitrogen. One obtains a clear, hard resin which softens at 70 C. and which is 1120 OH soluble in polar organic solvents. The constitution of this *OCHHB-CHz-O] resin may be rendered by the following formula:

me l1 g 0E2 OH Example 7 COCH2CHCHZO CH3 1 mol of resorcinol is heated with 2 mols of p-iso- C 3 1 m propenylphenyl glycidyl ether at 105-1l0 C., with the m means a Whole number greater than addition of 0.1% of sodium hydroxide. The mixture is maintained for a further hour at 150 C. and then cooled. PRODUCTION OF NOVEL COPOLYMERIZATES There is obtained a pale reddish-brown solid resin which E l 1 softens at 90 C. and is soluble in organic solvents. It 5 corresponds to the following formula: A Solution of 5 grams of a 2'hydroxy'l"(p'vinyl phenyl)-3-aryl-propylene diether, produced from 2 mols 0H of p-(l-methyl-vinyl)-phenylglycidyl ether (p-isopro- O-0CH -dl-Cfl 0 Q penylphenylglycidyl ether) and 1 mol of 2,2-di-(4-hyl 2 droxyphenyl)-propane of the formula 1 mol of hydroquinone is heated in an atmosphere of hydrogen at 110-115 C. with 2 mols of p-isopropenyl- 11,0 H

2 CH phenyl glycidyl ether, with the addition of 0.2% of sodia 1 1 1 2 in 95 grams of styrene is mixed with 0.2 gram of methyl hours, there is formed a hard, clear, insoluble and nonethyl ketone hydroperoxide and heated to 90 C. between meltable copolymerizate.

two glass plates rubbed with glycerol. After one hour, the solution has gelled and after a further four hours the hard mixed polymerizate is removed and tempered for A Solution of 25 grams of a Y y- -(P- Y a further five hours at 120 C. The copolymerizate is P 3' Y -P PY *diethel', Produced from 1 11101 Example 5 glass-clear, colorless, insoluble and non-meltable. It pos- 70f pp penyl gly y ether and 1 H101 of phenol 0f sesses outstanding mechanical and electrical properties. th f a The heat stability according to Martens amounts to 87 HZC\ OH O, the bonding strength according to Dynstat is 976 kg./ cm. the impact bond strength is 4.3 cm. kg./cm. and the in 75 grams of styrene is copolymerized at 80 C., with the addition of 0.4 gram of methyl ethyl ketone hydro- A solution of 25 grams of a 2-hydr0xy-1-(p-vinylperoxide. After 15 hours there is obtained a hard, clear, phenyl)3-aryl-propylene diether, produced from 2 mols insoluble and non-meltable copolymerizate. of p-isopropenyl-phenylglycidyl ether and 1 mol of 2,2- Example 6 di-(4-hydroxyphenyl)-propane, in 75 grams of styrene is mixed with 0.7 gram of cumyl hydroperoxide and 00- A Sohmon of 3 gram? of a 9 polymerized as described in Example 1 The copolymeriphenyl)'3 ary1'p?Opy1ene produceu from zfmols zate is glass-clear, almost colorless, insoluble and nonof ,p'lI'PhFnYIYmYI)'phenylglycldyl ether and 1 mol of meltable. It possesses outstanding mechanical and electri- 'dlhydroxydlphenyl sulfide of the formula cal properties. The heat stability according to Martens (1)11 amounts to 104 C., and the bonding strength according CO,CH2GCHO- to Dynstat is 1035 kg./cm. I S

Example 3 ball pressure hardness is 1415 kg./cm.

Example 2 A solution of 50 grams of a 2-hydroxy-1-(p-vinylphenyl)-3-aryl-propylene diether, produced from 2 mols of p-isopropenylphenyl glycidyl ether and 1 mol of ot,oc'- in 97 grams of acrylonitrile is copolymerized at 80 C. in di- (4-hydroxyphenyl)-a,a,a',a',-tetrarnethyl-p-xylene of a sealed ampoule, with the addition of 0.5; gram of dithe formula benzoyl peroxide. After 15 hours, there is formed a clear,

in grams of styrene is copolymerized at 90 C., after pale, yellowish, hard, insoluble and non-meltable copothe addition of 0.5 gram of cyclohexanone hydroperoxide. lymerizate. After fifteen hours, there is formed a hard, clear, insolu- E l xamp e 7 ble and non-meltable copolymerizlate.

A solution of 10 grams of a 2-hydroxy-1-(p-vinylphenyl)-3-aryl-propylene diether, produced from 2 mols A solution of 80 grams of a Z-hydroxy-l-(p-vinyl- 0f p-(l-ethylvinyl)-phenylglycidyl ether and l-mol of 1,1- phenyl)-3-aryl-propylene diether, produced from p-iso- 50 di-(4-hydroxyphenyl)-cyclohexanene of the formula Example 4 propenylphenyl glycidyl ether and the equivalent amount in 90 grams of methyl methacrylate is copolymerized at of cop-olymerizate) phenolic hydroxyl number 112 to 116) 80 C., with the addition of 0.5 gram of tertiary-butyl from p-isopropenylphenol and styrene of the formula perbenzotate. After 15 hours, there is obtained a colorless, glass-clear, hard, insoluble and non-meltable copolymerizate. g E Example 8 (F0113 A solution of 10 grams of a 2-hydroxy-1-(p-vinyl- H O H CH1 phenyl)-3-arylpropylene diether, produced from 2 mols @J of p-isopropenyl phenylglycidyl ether and 1 mol of 2,2-diz (4-hydroxyphenyl)-propane, and 30 grams of an unsatul rated polyester which contains, as main groups, maleic or fumaric acid residues, in 60 grams of styrene, to which 1 m means a whole number greater than 1 in '20 grams of gram of methyl ethyl ketone hydroperoxide and 2 grams styrene is copolymerized at 90 C., with the addition of of cobalt naphthalate are added, gells after standing for 0.8 gram of methyl ethyl ketone hydroperoxide. After 15 half an hour at room temperature. After a further 15 13 14 hours, there is obtained a clear, hard, insoluble and nonaromatic nuclei, and n is a whole number greater than 0. meltable copolymerizate. 2. Copolymerizates of the 2-hydroxy-1-(p-vinylphenyl)-3-aryl-propylene diether of claim 1 with ethylenically unsaturated compounds polymerizable across the double A solution of 60 grams of a 2-hydroxy-1-(p-vinyl- 5 bond.

pheny1)-3-aryl-propylene diether, produced from 200 3. A process for the production of copolymerizates grams'of a polyether (phenolic hydroxyl number 56) precomprising polymerizing the 2-hydroxy-1-(p-vinylphenyl)- pared from bis-phenol A and '2,2'-dichloro-diethyl ether S-aryl-propylene diether of claim 1 with an ethylenically and 38 grams of p-isopropenyl phenylglycidyl ether of the unsaturated compound polymerizable across the double formula bond.

Example 9 in grams of styrene is copolyrnerized at'80' C., after 4. A 2-hydroxy-1-(p-vinylphcnyl)-3-aryl-propylene dithe addition of 1 gram of dibenzoyl peroxide. After- 15 ether of claim '1 having the'formula:

hours, there is obtained a clear, colorless, hard, insoluble yl)-3-aryl-propylene diether of claim 2 having the forand non-meltable copolymerizate. mula We claim: 1. A 2-hydroxy-l-(p-vinylphenyD-B-aryl-propylene diether of the formula:

R4 R2 R1 0: OCHzCHOHCHr-O R0 with tyrene, R, 6. A 2-hydroXy-1-(p-vinylphenyl)-3-aryl-propylene di- 5 ether of claim 1 having the formula 0H l1 -0-omo-omo] H H5Cg ]& z

wherein R R and R are substituents selected from the 7. A copolymerizate of the 2-hydroxy-l-(p-vinylphengroup consisting of hydrogen, alkyl with up to 4 carbon yl)-3-aryl-propylene diether of claim 2 having the formula H2C\ on 11:13 I: C-O-CHaJJCHz-O] a CH: H30 H atoms, cyclo-alkyl and phenyl, R and R are substituents with styrene. selected from the group consisting of hydrogen and methyl, R is a radical with n substitutable hydroxyl groups on 9. A copolymerizate of the 2-hydroxy-1-(p-vinylphenyl)-3-ary1-pr0pylene diether of claim 2 having the formula with a solution of'a maleic acid unsaturated polyester in styrene.

References Cited UNITED STATES PATENTS 2/1961 DAlelio 26047 12/1962 Spence 26047 4/1966 Bruson 260613 JOSEPH L. SCHOFER, Primary Examiner.

25 M. B. KURTZMAN, Assistant Examiner. 

1. A 2-HYDROXY-1-(P-VINYLPHENYL)-3-ARYL-PROPYLENE DIETHER OF THE FORMULA 